Olefin(s) have traditionally been produced by steam or catalytic cracking of hydrocarbons. However, inevitably as oil resources decrease the price of oil will continue to increase; making light olefin(s) production a costly process. Thus there is an ever-growing need for non-petroleum routes to produce C2+ olefin(s), essentially ethylene and propylene. Such olefin(s) are useful starting materials for numerous chemical products including polymeric products such as polyethylene and polypropylene.
In recent years the search for alternative materials for C2+ olefin(s) production has led to the use of alcohols such as methanol, ethanol and higher alcohols. The said alcohols may be produced by the fermentation of, for example, sugars and/or cellulosic materials.
Alternatively, alcohols may be produced from synthesis gas (also known as “syngas”). Synthesis gas refers to a combination of hydrogen and carbon oxides produced in a synthesis gas plant from a carbon source such as natural gas, petroleum liquids, biomass and carbonaceous materials including coal, recycled plastics, municipal wastes, or any organic material. Thus, alcohol and alcohol derivatives may provide non-petroleum based routes for the production of olefin(s) and other related hydrocarbons.
Generally, the production of oxygenates, primarily methanol, takes place via three process steps. The three process steps are: synthesis gas preparation, methanol synthesis, and methanol purification. In the synthesis gas preparation step, an additional stage maybe employed by where the feedstock is treated, e.g. the feedstock is purified to remove sulfur and other potential catalyst poisons prior to being converted into synthesis gas. This additional stage can also be conducted after syngas preparation, e.g. when coal or biomass is employed.
Processes for producing mixtures of carbon oxide(s) and hydrogen (synthesis gas) are well known. Each has its advantages and disadvantages and the choice of using a particular reforming process is dictated by economic and available feed stream considerations, as well as by the desired mole ratio of H2:CO in the feedstock resulting from the reforming reaction. The synthesis gas may be prepared using any of the processes known in the art including partial oxidation of hydrocarbons, steam reforming, gas heated reforming, microchannel reforming (as described in, for example, U.S. Pat. No. 6,284,217), plasma reforming, autothermal reforming and any combination thereof. A discussion of these synthesis gas production technologies is provided in “Hydrocarbon Processing” V78, NA, 87-90, 92-93 (April 1999) and “Petrole et Techniques”, N. 415, 86-93 (July-August 1998). It is also known that the synthesis gas may be obtained by catalytic partial oxidation of hydrocarbons in a microstructured reactor as exemplified in “IMRET 3: Proceedings of the Third International Conference on Microreaction Technology”, Editor W Ehrfeld, Springer Verlag, 1999, pages 187-196. Alternatively, the synthesis gas may be obtained by short contact time catalytic partial oxidation of hydrocarbonaceous feedstocks as described in EP 0303438. Typically synthesis gas is obtained via a “Compact Reformer” process as described in “Hydrocarbon Engineering”, 2000, 5, (5), 67-69; “Hydrocarbon Processing”, 79/9, 34 (September 2000); “Today's Refinery”, 15/8, 9 (August 2000); WO 99/02254; and WO 200023689.
Typically, for commercial syngas production the pressure at which the synthesis gas is produced ranges from approximately 20 to 75 bar and the temperature at which the synthesis gas exits the reformer ranges from approximately 700 DEG C. to 1100 DEG C. The synthesis gas contains a molar ratio of hydrogen to carbon oxide—which is dependent on the syngas feedstock—ranging from 0.8 to 3.
Alcohol synthesis from syngas requires a H2:CO molar ratio which is typically between 1:1 and 2:1.
The applicants believe that the reaction of producing alcohol, such as ethanol, from synthesis gas can be written as so: 2CO+4H2→EtOH+H2O reaction stoichiometry 2:1 However, in addition to this the water gas shift reaction can also readily occur and thus the equilibrium under typical alcohol synthesis conditions strongly favours carbon dioxide and hydrogen production.CO+H2O=CO2+H2So the overall alcohol synthesis can be written as so:3CO+3H2→EtOH+CO2 reaction stoichiometry 1:1
In addition to this the water gas shift reaction allows CO2 and H2 to substitute for CO. So the required molar syngas ratio for alcohol synthesis can be written in terms of (H2-CO2):(CO+CO2) and in this case the required ratio is 2.
However, the H2:CO molar ratio used in practice is typically higher due to by-product formation, such as alkanes. The synthesis gas preparation, also know than those stated above, as reforming may take place in a single-step wherein all of the energy consuming and generating reforming reactions are accomplished. For example, in a single tubular steam reformer the reaction is overall endothermic whereas in autothermal reforming combustion of some of the feed and product is used to balance the heat duty. The single-step stream reformer usually results in the production of surplus hydrogen. In a preferred alternative, the synthesis gas preparation may take place in a two-step reforming process wherein the primary reforming in a tubular steam reformer is combined with an oxygen-fired secondary reforming step which if used in isolation produces a synthesis gas with a deficiency in hydrogen. With this combination it is possible to adjust the synthesis gas composition used, in order to obtain the most suitable composition for methanol synthesis. As an alternative, autothermal reforming results in a simplified process scheme with a lower capital cost. Autothermal reforming is where a stand-alone, oxygen-fired reformer first produces a hydrogen deficient synthesis gas, and then removes a least a portion of the carbon dioxide present, in order to obtain the desired molar ratio of hydrogen to carbon oxides.
The reaction from synthesis gas to oxygenates such as methanol is an exothermic equilibrium limited reaction. The conversion per pass to methanol is favored by low temperatures but a balance between rate and conversion must be maintained for economic considerations. It also requires high pressures over a heterogeneous catalyst, as the reactions which produce methanol exhibit a decrease in volume. As disclosed in U.S. Pat. No. 3,326,956, low-pressure methanol synthesis is based on a copper oxide-zinc oxide-alumina catalyst that typically operates at a nominal pressure of 5-10 MPa and temperatures ranging from approximately 150 DEG C. to 450 DEG C. over a variety of catalysts, including CuO/ZnO/Al2O3, CuO/ZnO/Cr2O3, ZnO/Cr2O3, Fe, Co, Ni, Ru, Os, Pt, and Pd. Catalysts based on ZnO for the production of methanol and dimethyl ether are preferred. The low-pressure, Copper-based methanol synthesis catalyst is commercially available from suppliers such as BASF, ICI Ltd. of the United Kingdom, and Haldor-Topsoe. Methanol yields from copper-based catalysts are generally over 99.5% of the converted CO+CO2 present. Water is a known by-product of the conversion of the synthesis gas to oxygenates. A paper entitled, “Selection of Technology for Large Methanol Plants,” by Helge Holm-Larsen, presented at the 1994 World Methanol Conference, Nov. 30-Dec. 1, 1994, in Geneva, Switzerland, and herein incorporated by reference, reviews the developments in methanol production and shows how further reduction in costs of methanol production will result in the construction of very large plants with capacities approaching 10,000 metric tonnes per day.
U.S. Pat. No. 4,543,435 discloses a process for converting an oxygenate feedstock comprising methanol, dimethyl ether or the like in an oxygenate conversion reactor into liquid hydrocarbons comprising C2-C4 olefin(s) and C5+ hydrocarbons. The C2-C4 olefin(s) are compressed to recover an ethylene-rich gas. The ethylene-rich gas is recycled to the oxygenate conversion reactor. U.S. Pat. No. 4,076,761 discloses a process for converting oxygenates to gasoline with the return of a hydrogen-rich gaseous product to a synthesis gas plant or the oxygenate conversion reaction zone.
U.S. Pat. No. 5,177,114 discloses a process for the conversion of natural gas to gasoline grade liquid hydrocarbons and/or olefin(s) by converting the natural gas to a synthesis gas, and converting the synthesis gas to crude methanol and/or dimethyl ether and further converting the crude methanol/dimethyl ether to gasoline and olefin(s).
International Patent Application No. 93/13013 to Kvisle et al relates to an improved method for producing a silicon-alumino-phosphate catalyst which is more stable to deactivation by coking. The patent discloses that after a period of time, all such catalysts used to convert methanol to olefin(s) (MTO) lose the active ability to convert methanol to hydrocarbons primarily because the microporous crystal structure is caked; that is, filled up with low volatility carbonaceous compounds which block the pore structure. The carbonaceous compounds can be removed by conventional methods such as combustion in air.
EPO publication No. 0 407 038A1 describes a method for producing dialkyl ethers comprising feeding a stream containing an alkyl alcohol to a distillation column reactor into a feed zone; contacting the stream with a fixed bed solid acidic catalytic distillation structure to form the corresponding dialkyl ether and water, and concurrently fractionating the ether product from the water and unreacted materials.
U.S. Pat. No. 5,817,906 describes a process for producing light olefin(s) from a crude oxygenate feedstock comprising alcohol and water. The process employs two reaction stages. Firstly, the alcohol is converted using reaction with distillation to an ether. The ether is then subsequently passed to an oxygenate conversion zone containing a metalaluminosilicate catalyst to produce a light olefin stream.
There is a well known chemistry that can be employed to produce olefin(s) from alcohol(s), i.e. the Methanol to olefin(s)—MTO-process (as described in Handbook of Petroleum refining processes third edition, Chapter 15.1 editor R. A. Meyers published by McGraw Hill).
This said MTO Process can be described as the dehydrative coupling of methanol to olefin(s). This mechanism is thought to proceed via a coupling of C1 fragments generated by the acid catalysed dehydration of methanol, possibly via a methyloxonium intermediate. However the main disadvantage of the said MTO process is that a range of olefin(s) are co-produced together with aromatic and alkane by-products, which in turn makes it very difficult and expensive to recover the desired olefin(s) at high purity.
Molecular sieves such as the microporous crystalline zeolite and non-zeolitic catalysts, particularly silicoaluminophosphates (SAPO), are known to promote the conversion of oxygenates by methanol to olefin (MTO) chemistry to hydrocarbon mixtures. Various patents describe the various types of these catalysts that may be used in this process, such as: U.S. Pat. Nos. 3,928,483, 4,025,575, 4,252,479 (Chang et al.); 4,496,786 (Santilli et al.); 4,547,616 (Avidan et al.); 4,677,243 (Kaiser); 4,843,183 (Inui); 4,499,314 (Seddon et al.); 4,447,669 (Harmon et al.); 5,095,163 (Barger); 5,191,141 (Barger); 5,126,308 (Barger); 4,973,792 (Lewis); and 4,861,938 (Lewis).
The MTO reaction has a high activation energy, possibly in the methanol or dimethyl ether activation step so in order to achieve reasonable rates there is often a need for high temperatures e.g. 300-450° C. However, unfortunately operating at these said high temperatures leads to major problems such as catalyst deactivation, coking and significant by-product formation. In order to minimize these problems the reactions may be operated at lower temperatures, but this necessitates larger reactors in addition to a large expensive recycle of intermediates and reactants.
Another major disadvantage associated with the MTO process is that the aromatic and alkcane by-products are co-produced together with the olefin(s) and are both difficult and expensive to separate from the desired products, e.g. separating ethylene and ethane is an expensive process.
These and other disadvantages of the prior art show that there is a need for an improved and/or alternative process for the production of C2 and C3 olefins from alcohols.
The solution to these and other disadvantages is provided by the present invention, which relates specifically to a new non-MTO process which proceeds via the dehydration of ethanol into olefins. This dehydration reaction is characterized in that carbon-carbon double bonds, are formed by elimination of water only and does not include the coupling of carbon fragments as is the case in MTO chemistry. It should be noted that for the dehydration of ethanol, by-products are formed. These can be formed by coupling of alkyl fragments e.g. acid catalysed olefin oligomerisation, such as:
2 propylene→Hexene
The by-products can also be formed by alcohol dehydrogenation, e.g. Ethanol→Acetaldehyde+H2 (J. Catalysis 1989, 117, pp 135-143 Y. Matsumura, K. Hashimoto and S. Yoshida).
The state of the hydrogen liberated may not be as free hydrogen but as chemisorbed hydrogen. Of particular relevance is the transfer hydrogenation reaction e.g.
Ethylene+H2→ethane
2 Ethanol→Acetaldehyde+ethane+water
The formation of same carbon number alkanes is known to add significantly to the complexity and cost of producing purified olefins for polymer manufacture. For example the industrially practiced catalytic cracking of hydrocarbon feedstocks to produce olefins for polymer manufacture is a capitally intensive process with a significant proportion of the cost involved in same number olefin and alkane separation. That is separation of ethane from ethylene and propane from propylene (as described in Handbook of Petroleum refining processes third edition, Chapter 3 editor R. A. Meyers published by McGraw Hill). This is also a disadvantage for the MTO process, (Ibid chapter 15.1). Dehydration of ethanol to ethylene has been commercially practiced in places such as Brazil; and India, albeit at a small scale. The reported reaction conditions are such that high conversion per pass to olefin is achieved at e.g. 1-2 barg, >350 C. It is a high selectivity process but produces unacceptable levels of alkanes for direct use in the preparation of polyethylene. Acceptable levels are often quoted as less than 500 ppm combined ethane and methane. Current practice of dehydration leads to olefins which need expensive purification before use in current polymerization processes, as is also the case with MTO.
U.S. Pat. No. 5,475,183 describes a process for producing light olefins by dehydrating lower alcohols having 2-4 carbon atoms on a alumina catalyst in the vapour phase. The typical reaction conditions given in the examples are 300-400 C at 8 to 18 Barg with reported olefin selectivities between 65 and 97%.
GB Pat No 2094829 describes how ethylene can be produced in a plurality of vapour phase adiabatic reactors with parts of the liquid products containing unconverted alcohol being recycled. The reaction conditions are described as the feed charge is at 400-520 C and a pressure 19-39 barg. The outlet product being kept at least 18 barg prior to being cryogenically purified. No examples were given of the predicted selectivity. U.S. Pat. No. 4,232,179 also describes how ethanol can be dehydrated in adiabatic reactors. The examples, with silica/alumina, and alumina show that the ethane content in the ethylene product is above 923-100000 ppm wt on ethylene. This is unacceptable for polyethylene production without additional purification.
DD Pat No 245866 describes how C2 to C4 olefins can be obtained from syngas-derived alcohol mixtures by vapour phase treatment with a zeolite catalyst between 300-500 C and 200-1000 kPa. Analysis of the examples has shown that significant conversion to C5 and higher hydrocarbons occurred. The examples describe the dehydration of mixtures of C1 to C7 alcohols. Example 1 describes the dehydration of a mixture of 76% methanol, 7.1% ethanol, 4.3% ethanol, 0.5% isopropanol, 4.3% n-propanol, 3.9% iso-butanol, 2% butanols, 2.1% amyl alcohol, 0.9% hexanols, 0.2% heptanols+balance other oxygenates to give 143.2 g ethylene, 96.8 g propene, 77.9 g butene, 174.3 g C5+ hydrocarbons. Clearly significant conversion of lower carbon moieties to higher carbon fragments is occurring on the modified zeolite catalyst.
U.S. Pat. No. 4,398,050 describes the synthesis of a mixed alcohol stream and purification to give a mixture of ethanol and propanol which is subsequently dehydrated at 0.5-1 bar, 350-500 C (example 1). The primary claim mentions the removal of methanol prior to dehydration, but not the removal of C4 and higher alcohols.
U.S. Pat. No. 4,423,270 describes the atmospheric pressure vapour phase dehydration of ethanol over a supported phosphoric acid catalyst with additional water and an alkyl substituted phosphoric acid. The reaction temperatures employed are between 300-400 C and the experiments were conducted at atmospheric pressure in a glass tube. The reported yields of ethylene ranged from 88-101%, no details of by-product formation was disclosed.
U.S. Pat. No. 4,727,214 describes the dehydration of ethanol over a crystalline aluminosilicate zeolite. The conditions claimed are between 1 and 10 bar and 126 and 526 C. Details of by-product formation are supplied to one decimal place and a selectivity to ethylene of 100% is reported. It is, however unclear from the patent if material suitable for polymer grade ethylene can be made without additional purification for removal of ethane.
Limited experimental information is available for n-propanol dehydration (Journal of Catalysis 169, 67-75 (1997) G. Larsen et al, J. Phy. Chem B 109/8 3345-3354), we have found that the dehydration proceeds in a similar manner to that reported for ethanol, with similar by-product formation e.g. alkanes, aldehydes, ketones, oligomers. The rate of oligomer formation is however more significant.